Dyestuffs derived from indoline bases and process for preparing same



Patented Apr. 22, 1930 e HEISSUED UNITED STATES PATENT oFF cE OTTMAR WAHL, OF LEVERKUSEN, GERMANY, ASSIGNOR TO GENERAL ANILINE 'W ORKS,-I1\TG., OF YORK, N. Y., A CORPORATION OF DELAWARE DYESTUFFS DERIVED FROM IND OLII IE BASES AND PROCESS FOR PREPARING SAME No Drawing. Application filed April 26, 1927, Serial No. 186,829, and in Germany May 3, 1926.

The present invention relates to new dyeusing tannin or other mordants, in beautiful stufi's derived from indoline bases and procgreenish yellow to reddish-orange shades of ess of preparing same. good fastness to light.

I have found that by treating a 1.3.3- The following-examples will illustrate our v trialkyl-Q-methylene indoline (such as 1.3.3- invention, all parts being by weight:

a I p 50 Egxethyl-Q-methylene indoline) of the for- Example 1 I 7 alkyl. One part of 1.3.3-trimethyl-2-methylene l,/ indoline (see Berichte der Deutschen Chem. I Gesellschaft, volume 23, page 2680, volume 5 31, page 612 and page GM) is dissolved in at 5 f 7 least 1 part of acetic-acid anhydride and 2 v lw parts of sodium nitrite are gradually added wherein the benzene nucleus may be substiwith Stirring Thgsolutiqn S001} becomes tuted or not or a salt thereof of the formula: tensely Yellow 0010 f Whlch p1 Ocess. m b 60 r J accelerated by heatmg. WVhen the lndohne alkyl has disappeared, the reaction mass is run into I d/alkyl water in order to destroy the acetic acid an L hydride, and the dyestufl' is salted .out with sod1um chl0r1de and Z1110 chlor1de, 1f neees- V x sary, wlth the addltion of sodlum blsulphite, I my] in order todestroy the excess of sodium nitrite. v The new dyestufi" has probably the wherein the benezene nucleus may be subst1- formula, tutedornot and X stafidsfor anorganic or I 5 inorganic acid radicle with an ester or a salt of r I 7 Y nitrous acid in the'presence of an organic acid i anhydride, as for example acetic anhydride d=on-N=on-d +znoh which serves as a condensing agent, there are 7 W produced new yellow to orange-reddyestufl's, 4 01/ H vwhich correspond probably to the general 1 v formula: It is, a clear, greenish-yellow body, which xy alkyl dyes-natural and artificial silk and cotton when using tannin or other mordants, in L ,L beautiful greenish-yellow shades of good fastness to light, to acids and t0 alkalies. In-

v f stead, of sodium nitrite for example, amyl L 1 1 51 4 nitrite can be employed; the reaction can also be carried out in the presence of a solvent. wherein the benzene nuelei ma be su stia tuted or not and X stands for afiorganic or Ewampze g inorganic acid radicle. 1 part of 5-amido-1-3.3-trimethyl-2-meth- The new dyestuffs are yellow to orangeylene indoline are mixed with 1 part of pow-- red crystalline powders soluble in water dered dry sodium nitrite and thennixture 1s with light yellow to orange-red color. They slowly brought into 2 parts of acetic acid 4 dye natuial and artificial silk and cotton when anhydride while stirring. Stirring is conprobably to the formula tinued'until the indoline has disappeared, then the reaction mass is run into water and the dyestufi, which dissolves in water with yellow-red color is salted out. It corresponds wherein X stands for an organic or inorganic acid radicle.

It is in a dry state an orange-red crystalline powder, easily soluble in water and diluted acids. 'It dyes natural and artificial silk and cotton when using tannin as mordant in reddish-yellow shades of quite good fast-mess to light. I

I wish it to be understood-that in the following claims one may use instead of a salt of the nitrous acid also an BStGPOf the nitrous acid, and instead of a 1.3.3-trialkyl-2-methylene indoline a salt thereof.

I claim: I

1. The process which consists in reacting with a salt of nitrous acid upona 1.3.3-trialkyl-Q-methlyne indoline of the general formula alkyl alkyl wherein the benezen nucleus may be substituted in the presence of acetic acid anhydride.

2. The process which consists in reacting with sodium nitrite upon 5-amino-1.3.3-trimethyl-Q-methlyene indoline of the probable formula HzN C-GH: =CH 3 I $3. a in the presence of acetic acid anhydride.

3. As new products dyestuffs corresponding probablyto the general formula:

alkyl wherein the benzene nuclei may be substituted or not and X stands for an organic or inorganic acid radicle, which are in a dry state yellow to orange-red crystalline powders,

soluble in water with light yellow to orange- NH(CHiOO) dHa i As new products the dyestuffs correwherein X stands for an organic or inorganic *acid radicle and wherein the benzene nuclei may be substituted, said-products being in 1 the dry state yellow to orange-red crystalline powders, soluble in water with light yellow ficial silk and cotton, when using tannin or other mordants, beautiful greenish-yellow to reddish-yellow shades of good fastness to light.-

5. As amew product a dyestufi corresponding probably to the general formula:

CHr-C (lO-CH:

N gidl 5 wherein X stands for an organic or inorganic acid radicle, which is 1n a dry state an orangeredcrystalhne powder, easily soluble in wa- .ter and diluted acids, and which dyes natural and artificial silk and cotton when using tannin as a mordant in reddish-yellow shades of quite good fastness to light.

In testimony whereof, I afligz my signature.

OTTMAR 'WAHL.

' to orange-red color dyeing natural and'arti- 

